JP2022529975A - Electrolyte membrane for all-solid-state battery and all-solid-state battery containing it - Google Patents

Electrolyte membrane for all-solid-state battery and all-solid-state battery containing it Download PDF

Info

Publication number
JP2022529975A
JP2022529975A JP2021561994A JP2021561994A JP2022529975A JP 2022529975 A JP2022529975 A JP 2022529975A JP 2021561994 A JP2021561994 A JP 2021561994A JP 2021561994 A JP2021561994 A JP 2021561994A JP 2022529975 A JP2022529975 A JP 2022529975A
Authority
JP
Japan
Prior art keywords
solid electrolyte
solid
electrolyte membrane
state battery
lithium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP2021561994A
Other languages
Japanese (ja)
Other versions
JP7263551B2 (en
Inventor
ジュン－ピル・イ
ウン－ビ・キム
ジ－フン・リュ
スク－ウ・イ
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LG Energy Solution Ltd
Original Assignee
LG Energy Solution Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by LG Energy Solution Ltd filed Critical LG Energy Solution Ltd
Publication of JP2022529975A publication Critical patent/JP2022529975A/en
Application granted granted Critical
Publication of JP7263551B2 publication Critical patent/JP7263551B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

本発明は、リチウムデンドライトの成長が抑制される固体電解質膜及びそれを含む全固体電池に関し、固体電解質材料及び金属粒子を含み、前記金属粒子はリチウムと合金化可能なものである。The present invention relates to a solid electrolyte membrane in which the growth of lithium dendrite is suppressed and an all-solid-state battery including the solid electrolyte film, which comprises a solid electrolyte material and metal particles, and the metal particles can be alloyed with lithium.

Description

本出願は、２０１９年４月１９日付け出願の韓国特許出願第１０－２０１９－００４６３１０号に基づく優先権を主張する。本発明は、リチウムデンドライトの成長を抑制することができる全固体電池用電解質膜及び該電解質膜を含む全固体電池に関する。 This application claims priority based on Korean Patent Application No. 10-2019-0046310, filed April 19, 2019. The present invention relates to an electrolyte membrane for an all-solid-state battery capable of suppressing the growth of lithium dendrite and an all-solid-state battery including the electrolyte membrane.

液体電解質を使用するリチウムイオン電池は、分離膜によって負極と正極とが区画される構造であるため、変形や外部の衝撃によって分離膜が損傷されれば短絡が生じ、それによって過熱または爆発などにつながるおそれがある。したがって、リチウムイオン二次電池の分野では、安全性を確保可能な固体電解質の開発が非常に重要な課題であると言える。 Lithium-ion batteries that use a liquid electrolyte have a structure in which the negative electrode and the positive electrode are separated by a separation film, so if the separation film is damaged by deformation or external impact, a short circuit will occur, which will cause overheating or explosion. There is a risk of connection. Therefore, in the field of lithium ion secondary batteries, it can be said that the development of a solid electrolyte that can ensure safety is a very important issue.

固体電解質を用いたリチウム二次電池は、電池の安全性が増大し、電解液の漏出を防止できるため電池の信頼性が向上し、薄型の電池を製作し易いという長所がある。また、負極としてリチウム金属を使用可能であるため、エネルギー密度を向上でき、それによって小型二次電池だけでなく電気自動車用高容量二次電池などへの応用が期待されて次世代電池として脚光を浴びている。 A lithium secondary battery using a solid electrolyte has the advantages that the safety of the battery is increased, the leakage of the electrolytic solution can be prevented, the reliability of the battery is improved, and it is easy to manufacture a thin battery. In addition, since lithium metal can be used as the negative electrode, the energy density can be improved, which is expected to be applied not only to small secondary batteries but also to high-capacity secondary batteries for electric vehicles, and is in the limelight as a next-generation battery. I'm bathing.

固体電解質材料としては、通常、高分子系固体電解質、酸化物系固体電解質及び硫化物系固体電解質材料が使用されている。このような固体電解質材料のみで薄膜の自立型（ｆｒｅｅ－ｓｔａｎｄｉｎｇ ｔｙｐｅ）電解質膜を製造する場合、電池の製造又は使用中に、裂けや割れが生じるか又は電解質材料が脱落するなどの不良が生じ得る。特に、負極活物質材料としてリチウム金属を使用する場合は、負極の表面からリチウムデンドライトが成長することがあり、成長したリチウムデンドライトが正極と接触すると電池の短絡が引き起こされる。図１は、このような固体電解質膜を正極と負極との間に介在して製造した全固体電池を示した図である。全固体電池では、分離膜の代わりに固体電解質膜が正極／負極の電気絶縁体の役割をしている。特に、固体電解質として高分子材料が使用される場合は、リチウムデンドライトの成長によって固体電解質膜が破損される場合がある。図１を参照すると、負極で成長したリチウムデンドライトによって固体電解質膜が損傷されて正極と負極との間に短絡が生じるおそれがある。また、無機固体電解質は、通常粒子状のイオン伝導性無機材料を集積して層状構造で形成したものであって、粒子同士の間のインタースティシャルボリューム（ｉｎｔｅｒｓｔｉｔｉａｌ ｖｏｌｕｍｅ）による気孔を多数含んでいる。これら気孔によって提供される空間にリチウムデンドライトが成長し得、気孔を通じて成長したリチウムデンドライトが正極と接触すれば、短絡が発生することになる。そこで、リチウムデンドライトの成長を抑制することができる全固体電池用電解質膜の開発が求められている。 As the solid electrolyte material, a polymer-based solid electrolyte, an oxide-based solid electrolyte, and a sulfide-based solid electrolyte material are usually used. When a thin film free-standing type electrolyte membrane is manufactured using only such a solid electrolyte material, defects such as tearing or cracking or the electrolyte material falling off occur during the manufacture or use of the battery. obtain. In particular, when lithium metal is used as the negative electrode active material, lithium dendrite may grow from the surface of the negative electrode, and when the grown lithium dendrite comes into contact with the positive electrode, a short circuit of the battery is caused. FIG. 1 is a diagram showing an all-solid-state battery manufactured by interposing such a solid electrolyte membrane between a positive electrode and a negative electrode. In the all-solid-state battery, the solid electrolyte film acts as an electrical insulator for the positive electrode / negative electrode instead of the separation film. In particular, when a polymer material is used as the solid electrolyte, the growth of lithium dendrite may damage the solid electrolyte membrane. Referring to FIG. 1, the lithium dendrite grown on the negative electrode may damage the solid electrolyte membrane and cause a short circuit between the positive electrode and the negative electrode. Inorganic solid electrolytes are usually formed by accumulating particulate ion-conducting inorganic materials in a layered structure, and contain a large number of pores due to the interstitial volume between the particles. .. Lithium dendrites can grow in the space provided by these pores, and if the lithium dendrites grown through the pores come into contact with the positive electrode, a short circuit will occur. Therefore, there is a demand for the development of an electrolyte membrane for an all-solid-state battery capable of suppressing the growth of lithium dendrite.

本発明は、上述した技術的課題を解決するためのものであって、リチウムデンドライトの成長が抑制される固体電解質膜及びそれを含む全固体電池を提供することを目的とする。一方、本発明の他の目的及び長所は、下記の説明によって理解できるであろう。また、本発明の目的及び長所は、特許請求の範囲に示される手段、方法またはその組合せによって実現することができる。 An object of the present invention is to solve the above-mentioned technical problems, and an object of the present invention is to provide a solid electrolyte membrane in which the growth of lithium dendrite is suppressed and an all-solid-state battery containing the same. On the other hand, other objects and advantages of the present invention may be understood by the following description. In addition, the objects and advantages of the present invention can be realized by means, methods or combinations thereof shown in the claims.

本発明は、上述した技術的課題を解決するための全固体電池用固体電解質膜に関する。本発明の第１態様は、ガイド層を含む固体電解質膜に関し、該固体電解質膜は、固体電解質材料及び金属粒子を含み、前記金属粒子はリチウムと合金化可能なものであり、前記ガイド層は前記固体電解質膜内に層状構造で配置され、前記金属粒子は前記ガイド層に含まれる。 The present invention relates to a solid electrolyte membrane for an all-solid-state battery for solving the above-mentioned technical problems. A first aspect of the present invention relates to a solid electrolyte membrane containing a guide layer, wherein the solid electrolyte membrane contains a solid electrolyte material and metal particles, the metal particles can be alloyed with lithium, and the guide layer is The metal particles are arranged in a layered structure in the solid electrolyte membrane, and the metal particles are included in the guide layer.

本発明の第２態様によれば、第１態様において、前記金属粒子はリチウム金属核生成過電位（Ｌｉ ｍｅｔａｌ ｎｕｃｌｅａｔｉｏｎ ｏｖｅｒｐｏｔｅｎｔｉａｌ）が１００ｍＶ以下のものである。 According to the second aspect of the present invention, in the first aspect, the metal particles have a lithium metal nucleation overpotential of 100 mV or less.

本発明の第３態様によれば、第１または第２態様において、前記固体電解質膜が金属粒子としてＡｕ、Ａｇ、Ｐｔ、Ｚｎ、Ｍｇ、Ａｌ、Ｎｉ、Ｂｉまたはこれらのうち二つ以上を含む。 According to the third aspect of the present invention, in the first or second aspect, the solid electrolyte membrane contains Au, Ag, Pt, Zn, Mg, Al, Ni, Bi or two or more of these as metal particles. ..

本発明の第４態様によれば、第１～第３態様のうちいずれか一つにおいて、前記ガイド層の厚さが１ｎｍ～１，０００ｎｍである。 According to the fourth aspect of the present invention, in any one of the first to third aspects, the thickness of the guide layer is 1 nm to 1,000 nm.

本発明の第５態様によれば、第１～第４態様のうちいずれか一つにおいて、前記固体電解質材料が高分子系固体電解質材料を含む。 According to the fifth aspect of the present invention, in any one of the first to fourth aspects, the solid electrolyte material includes a polymer-based solid electrolyte material.

本発明の第６態様によれば、第１～第５態様のうちいずれか一つにおいて、前記高分子系固体電解質材料が高分子樹脂及びリチウム塩を含み、１×１０－７Ｓ／ｃｍ以上のイオン伝導度を有する。 According to the sixth aspect of the present invention, in any one of the first to fifth aspects, the polymer-based solid electrolyte material contains a polymer resin and a lithium salt, and is 1 × 10 -7 S / cm or more. Has ionic conductivity of.

本発明の第７態様によれば、第１～第６態様のうちいずれか一つにおいて、前記金属粒子の粒径が１ｎｍ～５μｍである。 According to the seventh aspect of the present invention, in any one of the first to sixth aspects, the particle size of the metal particles is 1 nm to 5 μm.

本発明の第８態様によれば、第１～第７態様のうちいずれか一つにおいて、前記金属粒子が固体電解質膜１００重量％に対して０．１ｗｔ％～２０ｗｔ％の比率で含まれる。 According to the eighth aspect of the present invention, in any one of the first to seventh aspects, the metal particles are contained in a ratio of 0.1 wt% to 20 wt% with respect to 100% by weight of the solid electrolyte membrane.

また、本発明は、第１～第８態様のうちいずれか一つによる固体電解質膜を含む全固体電池に関する。 The present invention also relates to an all-solid-state battery including a solid electrolyte membrane according to any one of the first to eighth aspects.

ここで、前記全固体電池は、負極が負極活物質としてリチウム金属を含むか又は負極活物質なしに集電体のみからなり得る。 Here, in the all-solid-state battery, the negative electrode may contain a lithium metal as the negative electrode active material, or may consist only of a current collector without the negative electrode active material.

また、前記全固体電池は、負極、正極及び固体電解質膜を含み、前記固体電解質膜は負極と正極との間に介在され、前記負極及び正極の一つ以上は固体電解質材料を含み、前記固体電解質材料は高分子系固体電解質、酸化物系固体電解質、硫化物系固体電解質またはこれらのうち二つ以上を含み得る。 Further, the all-solid battery includes a negative electrode, a positive electrode and a solid electrolyte membrane, the solid electrolyte film is interposed between the negative electrode and the positive electrode, and one or more of the negative electrode and the positive electrode contains a solid electrolyte material, and the solid is contained. The electrolyte material may include a polymer-based solid electrolyte, an oxide-based solid electrolyte, a sulfide-based solid electrolyte, or two or more of them.

本発明の一態様による固体電解質膜は、固体電解質膜内にリチウムデンドライトの成長方向をガイドするガイド物質を含むガイド層が形成されている。前記ガイド物質は、リチウムと合金を形成可能な金属であって、これらがリチウムデンドライトの水平方向の成長を誘導する効果がある。これによって、負極でリチウムデンドライトが成長しても、それが垂直に成長して固体電解質膜を貫通するかまたはそれによって正極と接触することが防止される。それによって、負極活物質としてリチウム金属を含むリチウム金属電池に前記固体電解質膜が適用される場合、電池の寿命特性が改善される効果がある。 In the solid electrolyte membrane according to one aspect of the present invention, a guide layer containing a guide substance that guides the growth direction of lithium dendrite is formed in the solid electrolyte membrane. The guide material is a metal that can form an alloy with lithium, and these have the effect of inducing the horizontal growth of lithium dendrites. This prevents lithium dendrites from growing vertically at the negative electrode and penetrating the solid electrolyte membrane or thereby contacting the positive electrode. As a result, when the solid electrolyte membrane is applied to a lithium metal battery containing a lithium metal as a negative electrode active material, there is an effect of improving the life characteristics of the battery.

本明細書に添付される図面は、本発明の望ましい実施形態を例示するものであり、発明の内容とともに本発明の技術的な思想をさらに理解させる役割をするものであるため、本発明は図面に記載された事項だけに限定されて解釈されてはならない。一方、本明細書に添付される図面における要素の形状、大きさ、縮尺または比率などはより明確な説明を強調するため誇張されることもある。 The drawings attached to the present specification illustrate desirable embodiments of the present invention, and serve to further understand the technical idea of the present invention as well as the contents of the present invention. It should not be construed as being limited to the matters described in. On the other hand, the shape, size, scale or ratio of elements in the drawings attached herein may be exaggerated to emphasize a clearer explanation.

従来の固体電解質電池の断面構造を概略的に示した図である。It is a figure which showed schematic cross-sectional structure of the conventional solid electrolyte battery. 本発明による固体電解質膜の断面構造を概略的に示した図である。It is a figure which showed schematic cross-sectional structure of the solid electrolyte membrane by this invention. 図２のＡ部分の拡大図であり、垂直方向に成長したリチウムデンドライトが金属粒子と接して合金を形成した後、水平方向に成長するメカニズムを概略的に示した図である。It is an enlarged view of the part A of FIG. 2, and is the figure which schematically showed the mechanism which the lithium dendrite grown in the vertical direction comes into contact with metal particles to form an alloy, and then grows in the horizontal direction.

以下、本発明の具現例を詳しく説明する。これに先だち、本明細書及び特許請求の範囲に使われた用語や単語は通常的や辞書的な意味に限定して解釈されてはならず、発明者自らは発明を最善の方法で説明するために用語の概念を適切に定義できるという原則に則して本発明の技術的な思想に応ずる意味及び概念で解釈されねばならない。したがって、本明細書に記載された実施形態に示された構成は、本発明のもっとも望ましい一実施形態に過ぎず、本発明の技術的な思想のすべてを代弁するものではないため、本出願の時点においてこれらに代替できる多様な均等物及び変形例があり得ることを理解せねばならない。 Hereinafter, an embodiment of the present invention will be described in detail. Prior to this, the terms and words used in the present specification and the scope of the patent claim should not be construed in a general or lexical sense, and the inventor himself describes the invention in the best possible way. Therefore, it must be interpreted in the meaning and concept corresponding to the technical idea of the present invention in accordance with the principle that the concept of terms can be properly defined. Therefore, the configuration shown in the embodiments described herein is only one of the most desirable embodiments of the present invention and does not represent all of the technical ideas of the present invention. It must be understood that at some point there may be a variety of equivalents and variants that can replace them.

本明細書の全体において、ある部分が他の構成要素を「含む」とは、特に言及しない限り、他の構成要素を除くのではなく、他の構成要素をさらに含み得ることを意味する。 As used herein as a whole, the term "contains" to another component means that, unless otherwise noted, the other component may be further included rather than excluding the other component.

また、本明細書の全体で使われる用語「約」、「実質的に」などは、言及された意味に固有の製造及び物質許容誤差が提示されるとき、その数値でまたはその数値に近接した意味として使われ、本願の理解を助けるために正確又は絶対的な数値が言及された開示内容を非良心的な侵害者が不当に利用することを防止するために使われる。 Also, the terms "about", "substantially", etc. used throughout this specification are, or are close to, the numerical values when the manufacturing and material tolerances inherent in the referred meaning are presented. It is used as a meaning to prevent unscrupulous infringers from unfairly using disclosures that mention accurate or absolute numbers to aid in the understanding of the present application.

本明細書の全体において、「Ａ及び／またはＢ」との記載は「Ａ、Ｂまたはこれら全て」を意味する。 Throughout this specification, the term "A and / or B" means "A, B or all of these."

詳細な説明における特定の用語は便宜上使用されるものであって、制限的なものではない。「右」、「左」、「上面」及び「下面」の単語は参照する図面における方向を示す。「内側に」及び「外側に」の単語は、それぞれ指定された装置、システム及びその部材の幾何学的中心に向かう方向及びそれから遠くなる方向を示す。「前方」、「後方」、「上方」、「下方」及びその関連単語及び語句は、参照する図面における位置及び方位を示すものであって、制限的なものではない。このような用語は上記の単語、その派生語及び類似意味の単語を含む。 Specific terms in the detailed description are used for convenience and are not restrictive. The words "right", "left", "top" and "bottom" indicate the orientation in the referenced drawing. The words "inside" and "outside" indicate the direction towards and away from the geometric center of the specified device, system and its members, respectively. The terms "forward", "backward", "upward", "downward" and related words and phrases indicate the position and orientation in the reference drawing and are not restrictive. Such terms include the above words, their derivatives and words with similar meanings.

本発明は、全固体電池用電解質膜及びそれを含む全固体電池に関する。本発明による固体電解質膜は、リチウムデンドライトの垂直成長が抑制されて、特にリチウム金属を負極活物質として使用する電池に適用される場合、電池の寿命特性が著しく向上する効果がある。 The present invention relates to an electrolyte membrane for an all-solid-state battery and an all-solid-state battery including the same. The solid electrolyte membrane according to the present invention has an effect that the vertical growth of lithium dendrite is suppressed, and particularly when applied to a battery using a lithium metal as a negative electrode active material, the life characteristics of the battery are remarkably improved.

図２は、本発明による固体電解質膜を概略的に示した図である。これを参照して本発明の固体電解質膜を詳しく説明する。 FIG. 2 is a diagram schematically showing a solid electrolyte membrane according to the present invention. The solid electrolyte membrane of the present invention will be described in detail with reference to this.

本発明による固体電解質膜は、固体電解質材料及び金属粒子を含む。前記金属粒子は、リチウムデンドライトの成長方向を誘導（ガイド）するガイド物質であって、固体電解質膜内に層状構造（ｌａｙｅｒ ｓｈａｐｅ）を成しながら含まれる。図２は、本発明の一実施形態による固体電解質膜及びそれを含む全固体電池を概略的に示した図である。これによれば、固体電解質膜内にガイド層が含まれており、前記ガイド層はガイド物質を含む。以下、図２を参照して本発明を詳しく説明する。 The solid electrolyte membrane according to the present invention contains a solid electrolyte material and metal particles. The metal particles are guide substances that guide the growth direction of lithium dendrites, and are contained in the solid electrolyte membrane while forming a layered structure (layer shape). FIG. 2 is a diagram schematically showing a solid electrolyte membrane according to an embodiment of the present invention and an all-solid-state battery including the same. According to this, a guide layer is contained in the solid electrolyte membrane, and the guide layer contains a guide substance. Hereinafter, the present invention will be described in detail with reference to FIG.

本発明の一実施形態において、前記固体電解質膜は、全固体電池において正極と負極との間に介在されて絶縁及びイオン伝導性チャネルとして作用するものであって、望ましくは１．０×１０－７Ｓ／ｃｍ以上のイオン伝導度を有する。前記固体電解質膜は、固体電解質材料及びガイド物質である金属粒子を含み、前記金属粒子は固体電解質膜内に層状で含まれている。図２によれば、前記固体電解質膜には、厚さ方向で所定の深さにガイド層が配置され、前記ガイド物質である金属粒子は前記ガイド層に沿って分散して分布されている。 In one embodiment of the present invention, the solid electrolyte membrane is interposed between the positive electrode and the negative electrode in an all-solid-state battery and acts as an insulating and ionic conductive channel, preferably 1.0 × 10 − . It has an ionic conductivity of 7 S / cm or more. The solid electrolyte membrane contains metal particles which are a solid electrolyte material and a guide substance, and the metal particles are contained in a layer in the solid electrolyte membrane. According to FIG. 2, a guide layer is arranged at a predetermined depth in the thickness direction of the solid electrolyte membrane, and the metal particles as the guide substance are dispersed and distributed along the guide layer.

このように金属粒子が固体電解質膜の所定の深さに配置されたガイド層に配置されることで、金属粒子が電極活物質と直接接触せず離隔して位置でき、その結果、電極中の電極活物質の電気化学的性能の発揮には影響を及ぼさず、固体電解質膜内に浸透し成長したリチウムデンドライトの追加的な垂直成長のみを制御することができる。 By arranging the metal particles in the guide layer arranged at a predetermined depth of the solid electrolyte film in this way, the metal particles can be positioned apart from each other without directly contacting the electrode active material, and as a result, the metal particles in the electrode can be positioned. It does not affect the electrochemical performance of the electrode active material, and can only control the additional vertical growth of lithium dendrite that has penetrated and grown in the solid electrolyte membrane.

本発明において、前記金属粒子は、リチウムと反応して合金を形成可能なものである。また、前記金属粒子は、リチウムデンドライトの成長方向をガイドする役割を果たし、負極から正極側へと垂直に成長（すなわち、固体電解質膜の厚さ方向に沿って成長）するリチウムデンドライトと反応してリチウムデンドライトが水平方向に成長（すなわち、固体電解質膜の面方向に沿って成長）するように誘導する。すなわち、負極の表面で発生して正極側に成長するリチウムデンドライトが前記金属粒子と接触すると、デンドライトの成長が水平方向に転換される。本発明の一実施形態において、前記金属粒子は、例えば、Ａｕ、Ａｇ、Ｐｔ、Ｚｎ、Ｍｇ、Ａｌ、Ｎｉ、Ｂｉなどであり、本発明による固体電解質膜はこれらのうち少なくとも一つ以上を含むことができる。また、前記金属粒子は、リチウム金属核生成過電位が１００ｍＶ以下、望ましくは５０ｍＶ以下の値を有し得る。ここで、リチウム金属核生成過電位（Ｌｉ ｍｅｔａｌ ｎｕｃｌｅａｔｉｏｎ ｏｖｅｒｐｏｔｅｎｔｉａｌ）とは、リチウムと合金を形成するとき、電圧降下最低値と平坦電圧における平坦部分との差を意味する。過電位（ｏｖｅｒｐｏｔｅｎｔｉａｌ）が小さいほど、リチウムデンドライトとの接触時の合金形成の面で有利である。 In the present invention, the metal particles can react with lithium to form an alloy. In addition, the metal particles play a role of guiding the growth direction of the lithium dendrite and react with the lithium dendrite that grows vertically from the negative electrode to the positive electrode side (that is, grows along the thickness direction of the solid electrolyte film). Induces lithium dendrites to grow horizontally (ie, along the plane of the solid electrolyte membrane). That is, when the lithium dendrite generated on the surface of the negative electrode and growing on the positive electrode side comes into contact with the metal particles, the growth of the dendrite is converted in the horizontal direction. In one embodiment of the present invention, the metal particles are, for example, Au, Ag, Pt, Zn, Mg, Al, Ni, Bi and the like, and the solid electrolyte membrane according to the present invention contains at least one of these. be able to. Further, the metal particles may have a lithium metal nucleation superpotential of 100 mV or less, preferably 50 mV or less. Here, the lithium metal nucleation overpotential means the difference between the minimum voltage drop value and the flat portion at the flat voltage when forming an alloy with lithium. The smaller the overpotential, the more advantageous in terms of alloy formation upon contact with the lithium dendrite.

本発明の一実施形態において、前記金属粒子は粒径が１ｎｍ～５μｍである。例えば、前記粒径は１０ｎｍ～１μｍの範囲に調節され得る。粒径の大きさが上記の範囲に及ばなければリチウムデンドライトと接触して容易に合金を形成できるものの、ガイド層内に金属粒子が均一に分散し難い。一方、粒子の粒径が大き過ぎる場合は、合金を形成し難い。 In one embodiment of the present invention, the metal particles have a particle size of 1 nm to 5 μm. For example, the particle size can be adjusted in the range of 10 nm to 1 μm. If the size of the particle size does not fall within the above range, the alloy can be easily formed by contacting with lithium dendrite, but it is difficult for the metal particles to be uniformly dispersed in the guide layer. On the other hand, if the particle size of the particles is too large, it is difficult to form an alloy.

一方、本発明において、前記金属粒子は、リチウムデンドライトと接触した後、種結晶（ｓｅｅｄ ｃｒｙｓｔａｌ）が形成されるとき、安定的な構造になるように、球状または球状に近い類似球状であることが望ましい。しかし、球状や類似球状のみに限定されることはない。 On the other hand, in the present invention, the metal particles may be spherical or a similar spherical shape close to a spherical shape so as to have a stable structure when a seed crystal is formed after contact with lithium dendrite. desirable. However, it is not limited to a spherical shape or a similar spherical shape.

前記金属粒子は、固体電解質膜１００ｗｔ％に対して０．１ｗｔ％～２０ｗｔ％、望ましくは１ｗｔ％～１０ｗｔ％で含まれ得る。金属粒子の含量が上記の範囲を満足する場合、リチウムデンドライトの成長抑制及び寿命特性改善の効果が顕著であり、固体電解質膜のイオン伝導度を低下させない。 The metal particles may be contained in an amount of 0.1 wt% to 20 wt%, preferably 1 wt% to 10 wt% with respect to 100 wt% of the solid electrolyte membrane. When the content of the metal particles satisfies the above range, the effects of suppressing the growth of lithium dendrite and improving the life characteristics are remarkable, and the ionic conductivity of the solid electrolyte membrane is not lowered.

リチウムは、種結晶が生成されるエネルギーよりも樹枝状に成長するエネルギーが低いため、樹枝状成長するようになる。しかし、上述したように、リチウム金属核生成過電位が低い物質の場合、熱力学的にリチウムと類似である。したがって、固体電解質中に含まれた金属粒子が樹枝状に成長したリチウム金属と接触する場合、電気的に接続されて新たな種結晶を形成、すなわち金属粒子の周辺にリチウム合金を形成し、その後、形成された種結晶の表面で選択的にＬｉイオンが還元されてリチウムが析出される。このような析出時にリチウムが種結晶の周辺で成長するか又は水平方向に成長するようになる。 Lithium grows dendritic because it has a lower energy to grow dendritic than the energy to produce seed crystals. However, as mentioned above, in the case of a substance having a low lithium metal nucleation overpotential, it is thermodynamically similar to lithium. Therefore, when the metal particles contained in the solid electrolyte come into contact with the lithium metal grown in a dendritic shape, they are electrically connected to form a new seed crystal, that is, a lithium alloy is formed around the metal particles, and then. Lithium is selectively reduced on the surface of the formed seed crystal to precipitate lithium. At the time of such precipitation, lithium grows around the seed crystal or grows horizontally.

このように本発明による電解質膜は、リチウムデンドライトの成長によって電解質膜が貫通されることが抑制されるため、固体電解質膜の耐久性を向上させることができる。また、リチウムデンドライトが成長してもリチウムデンドライトが正極と接触する頻度が低くなるため、電池駆動中の短絡発生時点を著しく遅延させることができる。 As described above, the electrolyte membrane according to the present invention is prevented from being penetrated by the growth of lithium dendrite, so that the durability of the solid electrolyte membrane can be improved. Further, even if the lithium dendrite grows, the frequency of contact with the positive electrode of the lithium dendrite decreases, so that the time point at which a short circuit occurs during battery operation can be significantly delayed.

図２は、本発明による固体電解質膜を含む全固体電池を概略的に示した図である。前記全固体電池は、正極集電体１１０、正極活物質層１２０、固体電解質膜１３０、リチウム金属負極１４０が順次に積層された構造を有する。ここで、前記固体電解質膜内には金属粒子１３１が層状構造で含まれている。電池の駆動によってリチウム金属負極１４０からリチウムデンドライトが垂直方向に成長するが、これが金属粒子１３１と接触すると、図３に示されたように、金属粒子とリチウムとが合金を形成して種結晶１３１ａを生成し、その後、リチウムデンドライトが水平方向に成長する。図２において、リチウムデンドライトの垂直方向の成長は参照符号１４０ａで示し、水平方向の成長は１４０ｂで示した。図３は、図２のＡ部分の拡大図であり、種結晶の形成及びリチウムデンドライトの水平方向への成長を概略的に示した図である。 FIG. 2 is a diagram schematically showing an all-solid-state battery including a solid electrolyte membrane according to the present invention. The all-solid-state battery has a structure in which a positive electrode current collector 110, a positive electrode active material layer 120, a solid electrolyte film 130, and a lithium metal negative electrode 140 are sequentially laminated. Here, the metal particles 131 are contained in the solid electrolyte membrane in a layered structure. Lithium dendrite grows vertically from the lithium metal negative electrode 140 due to the drive of the battery, and when it comes into contact with the metal particles 131, as shown in FIG. 3, the metal particles and lithium form an alloy to form a seed crystal 131a. Then the lithium dendrite grows horizontally. In FIG. 2, the vertical growth of the lithium dendrite is indicated by reference numeral 140a and the horizontal growth is indicated by 140b. FIG. 3 is an enlarged view of a portion A of FIG. 2, which is a diagram schematically showing the formation of seed crystals and the horizontal growth of lithium dendrites.

本発明の一実施形態において、前記固体電解質材料は、イオン伝導度を有するものであって、高分子系固体電解質材料、酸化物系固体電解質材料、硫化物系固体電解質、またはこれらのうち二つ以上を含むことができる。 In one embodiment of the present invention, the solid electrolyte material has ionic conductivity, and is a polymer-based solid electrolyte material, an oxide-based solid electrolyte material, a sulfide-based solid electrolyte, or two of them. The above can be included.

前記高分子系固体電解質は、リチウム塩と高分子樹脂との複合物、すなわち、溶媒化したリチウム塩に高分子樹脂が添加されて形成された形態の高分子電解質材料であり、約１×１０－７Ｓ／ｃｍ以上、望ましくは約１×１０－５Ｓ／ｃｍ以上のイオン伝導度を有し得る。 The polymer-based solid electrolyte is a composite of a lithium salt and a polymer resin, that is, a polymer electrolyte material in a form formed by adding a polymer resin to a solvated lithium salt, and is about 1 × 10. It can have an ionic conductivity of -7 S / cm or higher, preferably about 1 x 10-5 S / cm or higher.

前記高分子樹脂の非制限的な例としては、ポリエーテル系高分子、ポリカーボネート系高分子、アクリレート系高分子、ポリシロキサン系高分子、ホスファゼン系高分子、ポリエチレン誘導体、ポリエチレンオキサイドのようなアルキレンオキサイド誘導体、リン酸エステルポリマー、ポリアジテーションリシン（ａｇｉｔａｔｉｏｎ ｌｙｓｉｎｅ）、ポリエステルスルファイド、ポリビニルアルコール、ポリフッ化ビニリデン、イオン性解離基を含む重合体などが挙げられ、これらのうち一つ以上を含むことができる。また、前記高分子系固体電解質は、高分子樹脂として、ポリエチレンオキサイド（ＰＥＯ）主鎖にポリメチルメタクリレート（ＰＭＭＡ）、ポリカーボネート、ポリシロキサン（ｐｄｍｓ）及び／またはホスファゼンのような無定形高分子を共単量体として共重合させた枝状共重合体、櫛状高分子樹脂（ｃｏｍｂ－ｌｉｋｅ ｐｏｌｙｍｅｒ）及び架橋高分子樹脂などのうち１種以上を含むことができる。 Non-limiting examples of the polymer resin include polyether polymers, polycarbonate polymers, acrylate polymers, polysiloxane polymers, phosphazenic polymers, polyethylene derivatives, and alkylene oxides such as polyethylene oxide. Examples thereof include derivatives, phosphate ester polymers, polyagitation lycines, polyester sulfides, polyvinyl alcohols, polyvinylidene fluorides, polymers containing ionic dissociation groups, and the like, and one or more of these can be contained. .. Further, the polymer-based solid electrolyte contains, as a polymer resin, an amorphous polymer such as polymethylmethacrylate (PMMA), polycarbonate, polysiloxane (pdms) and / or phosphazene in the main chain of polyethylene oxide (PEO). It can contain one or more of a branched copolymer copolymerized as a monomer, a comb-like polymer resin (comb-like polymer), a crosslinked polymer resin and the like.

本発明の電解質において、上述したリチウム塩は、イオン化可能なリチウム塩であって、Ｌｉ＋Ｘ－で表すことができる。このようなリチウム塩の陰イオンとしては、特に制限されないが、Ｆ－、Ｃｌ－、Ｂｒ－、Ｉ－、ＮＯ３ －、Ｎ（ＣＮ）２ －、ＢＦ４ －、ＣｌＯ４ －、ＰＦ６ －、（ＣＦ３）２ＰＦ４ －、（ＣＦ３）３ＰＦ３ －、（ＣＦ３）４ＰＦ２ －、（ＣＦ３）５ＰＦ－、（ＣＦ３）６Ｐ－、ＣＦ３ＳＯ３ －、ＣＦ３ＣＦ２ＳＯ３ －、（ＣＦ３ＳＯ２）２Ｎ－、（ＦＳＯ２）２Ｎ－ 、ＣＦ３ＣＦ２（ＣＦ３）２ＣＯ－、（ＣＦ３ＳＯ２）２ＣＨ－、（ＳＦ５）３Ｃ－、（ＣＦ３ＳＯ２）３Ｃ－、ＣＦ３（ＣＦ２）７ＳＯ３ －、ＣＦ３ＣＯ２ －、ＣＨ３ＣＯ２ －、ＳＣＮ－、（ＣＦ３ＣＦ２ＳＯ２）２Ｎ－などが挙げられる。 In the electrolyte of the present invention, the above-mentioned lithium salt is an ionizable lithium salt and can be represented by Li + X − . The anion of such a lithium salt is not particularly limited, but is F-, Cl- , Br- , I- , NO 3- , N (CN ) 2- , BF 4- , ClO 4- , PF 6- . , (CF 3 ) 2 PF 4- , (CF 3 ) 3 PF 3- , (CF 3 ) 4 PF 2- , (CF 3 ) 5 PF- , (CF 3 ) 6 P- , CF 3 SO 3- , CF 3 CF 2 SO 3- , (CF 3 SO 2 ) 2 N- , (FSO 2 ) 2 N- , CF 3 CF 2 (CF 3 ) 2 CO- , ( CF 3 SO 2 ) 2 CH- , (SF) 5 ) 3 C- , (CF 3 SO 2 ) 3 C- , CF 3 (CF 2 ) 7 SO 3- , CF 3 CO 2- , CH 3 CO 2- , SCN- , (CF 3 CF 2 SO 2 ) 2 N - etc.

前記酸化物系固体電解質材料は、酸素（Ｏ）を含み、周期表の第１族または第２族に属する金属のイオン伝導性を有するものである。その非制限的な例としては、ＬＬＴＯ系化合物、Ｌｉ６Ｌａ２ＣａＴａ２Ｏ１２、Ｌｉ６Ｌａ２ＡＮｂ２Ｏ１２（ＡはＣａまたはＳｒ）、Ｌｉ２Ｎｄ３ＴｅＳｂＯ１２、Ｌｉ３ＢＯ２．５Ｎ０．５、Ｌｉ９ＳｉＡｌＯ８、ＬＡＧＰ系化合物、ＬＡＴＰ系化合物、Ｌｉ１＋ｘＴｉ２－ｘＡｌｘＳｉｙ（ＰＯ４）３－ｙ（０≦ｘ≦１、０≦ｙ≦１）、ＬｉＡｌｘＺｒ２－ｘ（ＰＯ４）３（０≦ｘ≦１、０≦ｙ≦１）、ＬｉＴｉｘＺｒ２－ｘ（ＰＯ４）３（０≦ｘ≦１、０≦ｙ≦１）、ＬＩＳＩＣＯＮ系化合物、ＬＩＰＯＮ系化合物、ペロブスカイト系化合物、ＮＡＳＩＣＯＮ系化合物及びＬＬＺＯ系化合物から選択された１種以上を含むことができるが、これらに限定されることはない。 The oxide-based solid electrolyte material contains oxygen (O) and has ionic conductivity of a metal belonging to Group 1 or Group 2 of the periodic table. Non-limiting examples thereof include LLTO compounds, Li 6 La 2 CaTa 2 O 12 , Li 6 La 2 ANb 2 O 12 (A is Ca or Sr), Li 2 Nd 3 TeSbO 12 , Li 3 BO 2. 5 N 0.5 , Li 9 SiAlO 8 , LAGP-based compound, LATP-based compound, Li 1 + x Ti 2-x Al x Si y (PO 4 ) 3-y (0 ≦ x ≦ 1, 0 ≦ y ≦ 1), LiAl x Zr 2-x (PO 4 ) 3 (0 ≦ x ≦ 1, 0 ≦ y ≦ 1), LiTi x Zr 2-x (PO 4 ) 3 (0 ≦ x ≦ 1, 0 ≦ y ≦ 1), It can include, but is not limited to, one or more selected from LISION-based compounds, LIPON-based compounds, perovskite-based compounds, NASICON-based compounds and LLZO-based compounds.

前記硫化物系固体電解質材料は、硫黄（Ｓ）を含み、周期表の第１族または第２族に属する金属のイオン伝導性を有するものであって、Ｌｉ－Ｐ－Ｓ系ガラスやＬｉ－Ｐ－Ｓ系ガラスセラミックを含むことができる。このような硫化物系固体電解質の非制限的な例としては、Ｌｉ２Ｓ－Ｐ２Ｓ５、Ｌｉ２Ｓ－ＬｉＩ－Ｐ２Ｓ５、Ｌｉ２Ｓ－ＬｉＩ－Ｌｉ２Ｏ－Ｐ２Ｓ５、Ｌｉ２Ｓ－ＬｉＢｒ－Ｐ２Ｓ５、Ｌｉ２Ｓ－Ｌｉ２Ｏ－Ｐ２Ｓ５、Ｌｉ２Ｓ－Ｌｉ３ＰＯ４－Ｐ２Ｓ５、Ｌｉ２Ｓ－Ｐ２Ｓ５－Ｐ２Ｏ５、Ｌｉ２Ｓ－Ｐ２Ｓ５－ＳｉＳ２、Ｌｉ２Ｓ－Ｐ２Ｓ５－ＳｎＳ、Ｌｉ２Ｓ－Ｐ２Ｓ５－Ａｌ２Ｓ３、Ｌｉ２Ｓ－ＧｅＳ２、Ｌｉ２Ｓ－ＧｅＳ２－ＺｎＳ などが挙げられ、これらのうち一つ以上を含むことができるが、これらに限定されることはない。 The sulfide-based solid electrolyte material contains sulfur (S) and has ionic conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and is Li-PS-based glass or Li-. PS-based glass ceramics can be included. Non-limiting examples of such sulfide-based solid electrolytes include Li 2 SP 2 S 5, Li 2 S-LiI-P 2 S 5 , Li 2 S-LiI-Li 2 O-P 2 S. 5 , Li 2 S-LiBr-P 2 S 5 , Li 2 S-Li 2 O-P 2 S 5 , Li 2 S-Li 3 PO 4 -P 2 S 5 , Li 2 S-P 2 S 5 -P 2 O 5 , Li 2 S-P 2 S 5 -SiS 2 , Li 2 S-P 2 S 5 -SnS, Li 2 SP 2 S 5 -Al 2 S 3 , Li 2 S-GeS 2 , Li 2 Examples thereof include S-GeS 2 -ZnS, and one or more of these may be included, but the present invention is not limited thereto.

本発明の一実施形態において、前記固体電解質膜は、必要に応じてバインダー樹脂をさらに含むことができる。前記バインダー樹脂は、固体電解質材料同士の結着及び固体電解質膜とその両面に積層される電池要素（例えば、支持層及び／または電極）との結着のために導入される。バインダー樹脂の材料としては、特に限定されず、電気化学素子用結着剤として使用される成分の範囲内で適切に選択可能である。 In one embodiment of the present invention, the solid electrolyte membrane may further contain a binder resin, if necessary. The binder resin is introduced for binding the solid electrolyte materials to each other and to bond the solid electrolyte film and the battery element (for example, the support layer and / or the electrode) laminated on both sides thereof. The material of the binder resin is not particularly limited, and can be appropriately selected within the range of the components used as the binder for the electrochemical element.

本発明において、前記固体電解質膜は、約１００μｍ以下、望ましくは約１５μｍ～９０μｍの厚さを有する。前記固体電解質膜は、上述した範囲内でイオン伝導度、物理的強度、適用される電池のエネルギー密度などを考慮して適切な厚さを有し得る。例えば、イオン伝導度やエネルギー密度の面で、８０μｍ以下、７０μｍ以下、６０μｍ以下または５０μｍ以下の厚さを有し得る。一方、物理的強度の面で、２０μｍ以上、３０μｍ以上または４０μｍ以上の厚さを有し得る。また、前記固体電解質膜は、上記の厚さ範囲を有しながら、同時に約５００ｋｇｆ／ｃｍ２～約２，０００ｋｇｆ／ｃｍ２の引張強度を有し得る。また、前記固体電解質膜は、１５ｖｏｌ％以下または約１０ｖｏｌ％以下の気孔度を有し得る。 In the present invention, the solid electrolyte membrane has a thickness of about 100 μm or less, preferably about 15 μm to 90 μm. The solid electrolyte membrane may have an appropriate thickness within the above range in consideration of ionic conductivity, physical strength, energy density of the applied battery, and the like. For example, it may have a thickness of 80 μm or less, 70 μm or less, 60 μm or less, or 50 μm or less in terms of ionic conductivity and energy density. On the other hand, in terms of physical strength, it may have a thickness of 20 μm or more, 30 μm or more, or 40 μm or more. Further, the solid electrolyte membrane may have a tensile strength of about 500 kgf / cm 2 to about 2,000 kgf / cm 2 at the same time while having the above-mentioned thickness range. In addition, the solid electrolyte membrane may have a porosity of 15 vol% or less or about 10 vol% or less.

本発明による固体電解質膜は、上述した特徴を有する固体電解質膜を収得できる方法であれば、特に何れかの方法で製造されたものに限定されない。本発明の一実施形態において、前記固体電解質膜は、例えば二枚の固体電解質フィルムを用意した後、一方の固体電解質フィルムの表面にガイド層を形成し、該ガイド層が固体電解質膜の内部に配置されるように他方の固体電解質フィルムを積層し加圧して結合する方法で収得できる。 The solid electrolyte membrane according to the present invention is not particularly limited to that produced by any method as long as it can obtain the solid electrolyte membrane having the above-mentioned characteristics. In one embodiment of the present invention, for the solid electrolyte membrane, for example, after preparing two solid electrolyte films, a guide layer is formed on the surface of one of the solid electrolyte films, and the guide layer is inside the solid electrolyte membrane. It can be obtained by laminating the other solid electrolyte film so as to be arranged and pressing and bonding the other solid electrolyte film.

前記固体電解質フィルムは、固体電解質材料を含むイオン伝導性フィルムであって、例えば下記のような方法で収得することができる。 The solid electrolyte film is an ion conductive film containing a solid electrolyte material, and can be obtained by, for example, the following method.

まず、固体電解質材料を適切な溶媒に投入して固体電解質フィルム製造用分散液を用意する。 First, the solid electrolyte material is put into an appropriate solvent to prepare a dispersion liquid for producing a solid electrolyte film.

前記溶媒は、使用される固体電解質材料に合わせて適切なものが選択される。本発明の一実施形態において、前記溶媒は、Ｎ－メチルピロリドン（ＮＭＰ）、ジメチルホルムアミド（ＤＭＦ）、テトラヒドロフラン、ジメトキシエタン、ニトロメタン、アセトン、ピリジン、エタノール、アセトニトリル、ジメチルアセトアミドなどの有機溶媒または水などがあり、これら溶媒は単独でまたは２種以上を混合して使用することができる。例えば、高分子樹脂としてＰＥＯのようなアルキレンオキサイド系を使用する場合は、溶媒としてアセトニトリルを使用できる。次いで、前記分散液をテレフタレートフィルムなどの離型シートに塗布して所定の厚さを有するフィルムの形状に成形する。塗布及び成形は、ドクターブレードのような公知のコーティング方法を使用できる。その後、乾燥して溶媒を除去し、固体電解質フィルムを収得する。 An appropriate solvent is selected according to the solid electrolyte material used. In one embodiment of the invention, the solvent may be an organic solvent such as N-methylpyrrolidone (NMP), dimethylformamide (DMF), tetrahydrofuran, dimethoxyethane, nitromethane, acetone, pyridine, ethanol, acetonitrile, dimethylacetamide, or water. These solvents can be used alone or in admixture of two or more. For example, when an alkylene oxide system such as PEO is used as the polymer resin, acetonitrile can be used as the solvent. Next, the dispersion liquid is applied to a release sheet such as a terephthalate film to form a film having a predetermined thickness. For coating and molding, a known coating method such as a doctor blade can be used. Then, it dries to remove the solvent, and a solid electrolyte film is obtained.

また、本発明の一実施形態において、前記ガイド層は、下記のように形成することができる。まず、金属粒子を溶媒に投入してガイド層形成用分散液を用意し、該分散液を上述した方法によって製造された固体電解質フィルムの表面に塗布する。本発明の一実施形態において、前記分散液は固体電解質材料をさらに含むことができる。このような場合、ガイド層は金属粒子と固体電解質材料とが混合された混合物を含み、ガイド層にイオン伝導度を与えることができる。本発明の一実施形態において、前記溶媒は、ＮＭＰ、ＤＭＦ、テトラヒドロフラン、ジメトキシエタン、ニトロメタン、アセトン、ピリジン、エタノール、アセトニトリル、ジメチルアセトアミドなどの有機溶媒または水などがあり、これら溶媒を単独でまたは２種以上を混合して使用することができる。 Further, in one embodiment of the present invention, the guide layer can be formed as follows. First, the metal particles are put into a solvent to prepare a dispersion liquid for forming a guide layer, and the dispersion liquid is applied to the surface of the solid electrolyte film produced by the above-mentioned method. In one embodiment of the invention, the dispersion may further comprise a solid electrolyte material. In such a case, the guide layer contains a mixture of metal particles and a solid electrolyte material, and can impart ionic conductivity to the guide layer. In one embodiment of the invention, the solvent may be an organic solvent such as NMP, DMF, tetrahydrofuran, dimethoxyethane, nitromethane, acetone, pyridine, ethanol, acetonitrile, dimethylacetamide or water, these solvents alone or 2 More than seeds can be mixed and used.

前記分散液をフィルムの表面に塗布する方法は、スリットダイ（ｓｌｉｔ ｄｉｅ）コーティング、ディップ（ｄｉｐ）コーティング、グラビア（ｇｒａｖｕｒｅ）コーティング、スピン（ｓｐｉｎ）コーティング、ロール（ｒｏｌｌ）コーティング、バー（ｂａｒ）コーティング、スプレー（ｓｐｒａｙ）コーティング、フロー（ｆｌｏｗ）コーティングなど公知の塗布方法から適切な一つ以上の方法を選択して適用することができる。その後、分散液を乾燥して溶媒を除去し、フィルムの表面にガイド層を形成する。 The method of applying the dispersion liquid to the surface of the film includes slit die coating, dip coating, gravure coating, spin coating, roll coating, and bar coating. , One or more suitable coating methods can be selected and applied from known coating methods such as spray coating and flow coating. Then, the dispersion is dried to remove the solvent, and a guide layer is formed on the surface of the film.

本発明の一実施形態において、前記ガイド層の厚さは１ｎｍ～１，０００ｎｍである。また、前記ガイド層は、フィルムの表面積１００％に対して５％～８０％、望ましくは１０％～６０％の面積比率で被覆されることが望ましい。前記ガイド層の被覆面積が広過ぎれば、ガイド層の上部及び下部へのイオン伝導が遮断されて固体電解質膜のイオン伝導度特性が低下するおそれがある。一方、被覆面積が狭いと、反応確率が低くて所望の効果を達成し難い。このように一方の固体電解質フィルムの表面にガイド層を形成した後、他方の固体電解質フィルムをガイド層上に積層し、二枚の電解質フィルムを加圧して結合する。このような方法で図２に示された構造の固体電解質膜を収得できる。 In one embodiment of the present invention, the thickness of the guide layer is 1 nm to 1,000 nm. Further, it is desirable that the guide layer is covered with an area ratio of 5% to 80%, preferably 10% to 60% with respect to 100% of the surface area of the film. If the covering area of the guide layer is too large, the ionic conduction to the upper part and the lower part of the guide layer may be blocked and the ionic conductivity characteristics of the solid electrolyte membrane may be deteriorated. On the other hand, if the covering area is small, the reaction probability is low and it is difficult to achieve the desired effect. After forming the guide layer on the surface of one solid electrolyte film in this way, the other solid electrolyte film is laminated on the guide layer, and the two electrolyte films are pressed and bonded. By such a method, the solid electrolyte membrane having the structure shown in FIG. 2 can be obtained.

また、本発明は、上述した固体電解質膜を含む全固体電池を提供する。前記全固体電池は、正極、負極及び固体電解質膜を含む。本発明の一実施形態において、前記負極は、負極活物質としてリチウム金属を含むことができる。 The present invention also provides an all-solid-state battery including the above-mentioned solid electrolyte membrane. The all-solid-state battery includes a positive electrode, a negative electrode, and a solid electrolyte membrane. In one embodiment of the present invention, the negative electrode may contain a lithium metal as the negative electrode active material.

本発明において、正極及び負極は、集電体及び該集電体の少なくとも一面に形成された電極活物質層を含み、前記電極活物質層は複数の電極活物質粒子及び固体電解質材料を含む。また、それぞれの電極は、必要に応じて導電材及びバインダー樹脂のうち一つ以上をさらに含むことができる。また、前記電極は、電極の物理化学的特性の補完や改善を目的として、多様な添加剤をさらに含むことができる。 In the present invention, the positive electrode and the negative electrode include a current collector and an electrode active material layer formed on at least one surface of the current collector, and the electrode active material layer contains a plurality of electrode active material particles and a solid electrolyte material. Further, each electrode may further contain one or more of the conductive material and the binder resin, if necessary. Further, the electrode may further contain various additives for the purpose of complementing or improving the physicochemical properties of the electrode.

本発明において、負極活物質としては、リチウムイオン二次電池の負極活物質としてリチウム金属を含むことができ、他にも負極活物質として使用可能な物質であれば何れも使用できる。例えば、前記負極活物質は、難黒鉛化炭素、黒鉛系炭素などの炭素；ＬｉｘＦｅ２Ｏ３（０≦ｘ≦１）、ＬｉｘＷＯ２（０≦ｘ≦１）、ＳｎｘＭｅ１－ｘＭｅ’ ｙＯｚ（Ｍｅ：Ｍｎ、Ｆｅ、Ｐｂ、Ｇｅ；Ｍｅ’：Ａｌ、Ｂ、Ｐ、Ｓｉ、周期表の１族、２族、３族元素、ハロゲン；０＜ｘ≦１；１≦ｙ≦３；１≦ｚ≦８）などの金属複合酸化物；リチウム合金；ケイ素系合金；スズ系合金；ＳｎＯ、ＳｎＯ２、ＰｂＯ、ＰｂＯ２、Ｐｂ２Ｏ３、Ｐｂ３Ｏ４、Ｓｂ２Ｏ３、Ｓｂ２Ｏ４、Ｓｂ２Ｏ５、ＧｅＯ、ＧｅＯ２、Ｂｉ２Ｏ３、Ｂｉ２Ｏ４及びＢｉ２Ｏ５などの金属酸化物；ポリアセチレンなどの導電性高分子；Ｌｉ－Ｃｏ－Ｎｉ系材料；チタン酸化物；リチウムチタン酸化物などから選択された１種または２種以上を使用することができる。 In the present invention, the negative electrode active material can include lithium metal as the negative electrode active material of the lithium ion secondary battery, and any other substance that can be used as the negative electrode active material can be used. For example, the negative electrode active material is a carbon refractory carbon, a graphite-based carbon, or other carbon; Li x Fe 2 O 3 (0 ≦ x ≦ 1), Li x WO 2 (0 ≦ x ≦ 1), Sn x Me 1 . -X Me'y Oz ( Me: Mn, Fe, Pb, Ge ; Me' : Al, B, P, Si, Group 1 and Group 2 and Group 3 elements of the periodic table, halogen; 0 <x≤1; 1 ≦ y ≦ 3; 1 ≦ z ≦ 8) and other metal composite oxides; lithium alloys; silicon alloys; tin alloys; SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Metal oxides such as Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3 , Bi 2 O 4 and Bi 2 O 5 ; Conductive polymers such as polyacetylene; Li- One or more selected from Co—Ni-based materials; titanium oxides; lithium titanium oxides and the like can be used.

前記電極が正極である場合、電極活物質は、リチウムイオン二次電池の正極活物質として使用可能なものであれば制限なく使用できる。例えば、前記正極活物質としては、リチウムコバルト酸化物（ＬｉＣｏＯ２）、リチウムニッケル酸化物（ＬｉＮｉＯ２）などの層状化合物、または、一つまたはそれ以上の遷移金属で置換された化合物；化学式Ｌｉ１＋ｘＭｎ２－ｘＯ４（ｘは０～０．３３）、ＬｉＭｎＯ３、ＬｉＭｎ２Ｏ３、ＬｉＭｎＯ２などのリチウムマンガン酸化物；リチウム銅酸化物（Ｌｉ２ＣｕＯ２）；ＬｉＶ３Ｏ８、ＬｉＶ３Ｏ４、Ｖ２Ｏ５、Ｃｕ２Ｖ２Ｏ７などのバナジウム酸化物；化学式ＬｉＮｉ１－ｘＭｘＯ２（Ｍ＝Ｃｏ、Ｍｎ、Ａｌ、Ｃｕ、Ｆｅ、Ｍｇ、ＢまたはＧａ、ｘ＝０．０１～０．３）で表されるＮｉサイト型リチウムニッケル酸化物；化学式ＬｉＭｎ１－ｘＭｘＯ２（Ｍ＝Ｃｏ、Ｎｉ、Ｆｅ、Ｃｒ、ＺｎまたはＴａ、ｘ＝０．０１～０．１）またはＬｉ２Ｍｎ３ＭＯ８（Ｍ＝Ｆｅ、Ｃｏ、Ｎｉ、ＣｕまたはＺｎ）で表されるリチウムマンガン複合酸化物；ＬｉＮｉｘＭｎ２－ｘＯ４で表されるスピネル構造のリチウムマンガン複合酸化物；化学式のＬｉの一部がアルカリ土類金属イオンで置換されたＬｉＭｎ２Ｏ４；ジスルフィド化合物；Ｆｅ２（ＭｏＯ４）３などが挙げられるが、これらに限定されることはない。 When the electrode is a positive electrode, the electrode active material can be used without limitation as long as it can be used as the positive electrode active material of the lithium ion secondary battery. For example, the positive electrode active material may be a layered compound such as lithium cobalt oxide (LiCoO 2 ) or lithium nickel oxide (LiNiO 2 ), or a compound substituted with one or more transition metals; chemical formula Li 1 + x. Lithium manganese oxides such as Mn 2-x O 4 (x is 0 to 0.33), LiMnO 3 , LiMn 2 O 3 , LiMnO 2 ; Lithium copper oxide (Li 2 CuO 2 ); LiV 3 O 8 , LiV Vanadium oxides such as 3 O 4 , V 2 O 5 , Cu 2 V 2 O 7 ; Chemical formula LiNi 1-x M x O 2 (M = Co, Mn, Al, Cu, Fe, Mg, B or Ga, x Nisite-type lithium nickel oxide represented by (= 0.01 to 0.3); Chemical formula LiMn 1-x M x O 2 (M = Co, Ni, Fe, Cr, Zn or Ta, x = 0.01) ~ 0.1) or Lithium-manganese composite oxide represented by Li 2 Mn 3 MO 8 (M = Fe, Co, Ni, Cu or Zn); Spinel structure represented by LiNi x Mn 2-x O4 Limn 2 O 4 in which a part of Li of the chemical formula is replaced with an alkaline earth metal ion; a disulfide compound; Fe 2 (MoO 4 ) 3 and the like can be mentioned, but the present invention is not limited thereto. do not have.

本発明において、前記集電体は、金属板などの電気伝導性を有して二次電池分野で公知の集電体を、電極の極性に合わせて適切に使用することができる。 In the present invention, as the current collector, a current collector having electrical conductivity such as a metal plate and known in the field of secondary batteries can be appropriately used according to the polarity of the electrode.

本発明において、前記導電材は、通常、電極活物質を含む混合物の全体重量を基準にして１～３０ｗｔ％で添加される。このような導電材は、当該電池に化学的変化を誘発せず導電性を有するものであれば特に制限されなく、例えば、天然黒鉛や人造黒鉛などの黒鉛；カーボンブラック、アセチレンブラック、ケッチェンブラック、チャンネルブラック、ファーネスブラック、ランプブラック、サーマルブラックなどのカーボンブラック類；炭素繊維や金属繊維などの導電性繊維；フッ化カーボン、アルミニウム、ニッケル粉末などの金属粉末；酸化亜鉛、チタン酸カリウムなどの導電性ウィスカー；酸化チタンなどの導電性金属酸化物；ポリフェニレン誘導体などの導電性素材から選択された１種または２種以上の混合物を含むことができる。 In the present invention, the conductive material is usually added in an amount of 1 to 30 wt% based on the total weight of the mixture containing the electrode active material. Such a conductive material is not particularly limited as long as it does not induce a chemical change in the battery and has conductivity, for example, graphite such as natural graphite or artificial graphite; carbon black, acetylene black, ketjen black. , Carbon blacks such as channel black, furnace black, lamp black, thermal black; conductive fibers such as carbon fiber and metal fiber; metal powder such as carbon fluoride, aluminum and nickel powder; zinc oxide, potassium titanate, etc. It can contain one or more mixtures selected from conductive materials such as conductive whiskers; conductive metal oxides such as titanium oxide; polyphenylene derivatives and the like.

本発明において、前記バインダー樹脂は、活物質と導電材などとの結合、及び集電体に対する結合を補助する成分であれば特に制限されず、例えばポリフッ化ビニリデン、ポリビニルアルコール、カルボキシメチルセルロース（ＣＭＣ）、澱粉、ヒドロキシプロピルセルロース、再生セルロース、ポリビニルピロリドン、テトラフルオロエチレン、ポリエチレン、ポリプロピレン、エチレン－プロピレン－ジエンモノマー（ＥＰＤＭ）、スルホン化ＥＰＤＭ、スチレンブタジエンゴム、フッ素ゴム、多様な共重合体などが挙げられる。前記バインダー樹脂は、通常、電極層１００ｗｔ％に対して１～３０ｗｔ％、または１～１０ｗｔ％の範囲で含むことができる。 In the present invention, the binder resin is not particularly limited as long as it is a component that assists the bond between the active material and the conductive material and the bond to the current collector, and is, for example, polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC). , Stool, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene monomer (EPDM), sulfonated EPDM, styrene butadiene rubber, fluororubber, various copolymers, etc. Be done. The binder resin can usually be contained in the range of 1 to 30 wt% or 1 to 10 wt% with respect to 100 wt% of the electrode layer.

一方、本発明において、それぞれの電極活物質層は、必要に応じて酸化安定添加剤、還元安定添加剤、難燃剤、熱安定剤、防曇剤（ａｎｔｉｆｏｇｇｉｎｇ ａｇｅｎｔ）などのような添加剤を１種以上含むことができる。 On the other hand, in the present invention, each electrode active material layer contains one additive such as an oxidation stabilizing additive, a reduction stabilizing additive, a flame retardant, a heat stabilizer, and an antifogging agent, if necessary. Can contain more than a seed.

本発明において、前記電極に含まれる固体電解質材料は、高分子系固体電解質、酸化物系固体電解質及び硫化物系固体電解質のうち一つ以上を含むことができ、各電解質材料については上述した説明を参照できる。 In the present invention, the solid electrolyte material contained in the electrode may contain one or more of a polymer-based solid electrolyte, an oxide-based solid electrolyte, and a sulfide-based solid electrolyte, and each electrolyte material will be described above. Can be referred to.

前記固体電解質材料において、正極の場合は、固体電解質として酸化安定性に優れた電解質材料を使用することができる。また、負極の場合は、固体電解質として還元安定性に優れた電解質材料を使用することができる。しかし、これらに限定されるものではなく、電極で主にリチウムイオンを伝達する役割をするため、イオン伝導度の高い素材、例えば、１０－７Ｓ／ｍ以上または１０－５Ｓ／ｍ以上のものであれば何れも使用可能であり、特定の成分に限定されない。 In the case of the positive electrode in the solid electrolyte material, an electrolyte material having excellent oxidative stability can be used as the solid electrolyte. Further, in the case of the negative electrode, an electrolyte material having excellent reduction stability can be used as the solid electrolyte. However, the present invention is not limited to these, and since the electrode mainly plays a role of transmitting lithium ions, a material having high ionic conductivity, for example, 10-7 S / m or more or 10-5 S / m or more. Any of these can be used and is not limited to a specific component.

また、本発明は、上述した構造を有する二次電池を提供する。また、本発明は、前記二次電池を単位電池として含む電池モジュール、前記電池モジュールを含む電池パック、及び前記電池パックを電源として含むデバイスを提供する。このとき、前記デバイスの具体的な例としては、電気モーターによって動力を受けて駆動するパワーツール；電気自動車（Ｅｌｅｃｔｒｉｃ Ｖｅｈｉｃｌｅ：ＥＶ）、ハイブリッド電気自動車（Ｈｙｂｒｉｄ Ｅｌｅｃｔｒｉｃ Ｖｅｈｉｃｌｅ：ＨＥＶ）、プラグインハイブリッド電気自動車（Ｐｌｕｇ－ｉｎ Ｈｙｂｒｉｄ Ｅｌｅｃｔｒｉｃ Ｖｅｈｉｃｌｅ：ＰＨＥＶ）などを含む電気車；電気自転車（Ｅ－ｂｉｋｅ）、電気スクーター（Ｅ－ｓｃｏｏｔｅｒ）を含む電気二輪車；電気ゴルフカート；電力貯蔵用システムなどが挙げられるが、これらに限定されることはない。 The present invention also provides a secondary battery having the above-mentioned structure. The present invention also provides a battery module containing the secondary battery as a unit battery, a battery pack including the battery module, and a device including the battery pack as a power source. At this time, specific examples of the device include a power tool powered by an electric motor; an electric vehicle (EV), a hybrid electric vehicle (HEV), and a plug-in hybrid electric vehicle. (Plug-in Hybrid Electric Vehicle: PHEV) and the like; electric vehicles including electric bicycles (E-bikes), electric scooters (E-scootters); electric golf carts; power storage systems, etc. It is not limited to these.

以下、実施例を挙げて本発明をより詳しく説明するが、下記の実施例は本発明を例示するためのものであって、本発明の範疇がこれらに限定されることはない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the following examples are for exemplifying the present invention, and the scope of the present invention is not limited thereto.

実施例１
１．電解質フィルムの製造
以下の方法で電解質フィルムを製造した。溶媒としてアセトニトリル（ＡＮ）にポリエチレンオキサイド（Ｍｗ＝４，０００，０００ｇ／ｍｏｌ）を溶かして４ｗｔ％の高分子溶液を用意した。このとき、リチウム塩としてＬｉＴＦＳＩを［ＥＯ］／［Ｌｉ＋］＝１８／１（モル比）になるように一緒に投入した。前記高分子溶液をＰＥＯ及びリチウム塩が十分に溶けるように６０℃で一晩撹拌した。次いで、開始剤と硬化剤を含む添加剤溶液を用意した。硬化剤としてはポリエチレングリコールジアクリレート（ＰＥＧＤＡ、Ｍｗ＝５７５）、開始剤としては過酸化ベンゾイル（ＢＰＯ）を使用し、ＰＥＧＤＡはＰＥＯ対比２０ｗｔ％、ＢＰＯはＰＥＧＤＡ対比１ｗｔ％の量になるようにし、溶媒としてはアセトニトリルを使用した。前記添加剤溶液を投入した成分が十分に混合されるように約１時間撹拌した。その後、前記添加剤溶液を前記高分子溶液に添加し、二つの溶液を十分に混合した。混合した溶液を離型フィルムにドクターブレードを用いて塗布及びコーティングした。コーティングギャップは８００μｍ、コーティング速度は２０ｍｍ／ｍｉｎにした。前記溶液がコーティングされた離型フィルムをガラス板に移し、水平を維持しながら常温条件で一晩乾燥し、１００℃で１２時間真空乾燥した。このような方式で電解質フィルムをそれぞれ二枚収得した。収得されたそれぞれの電解質フィルムの厚さは約５０μｍであった。 Example 1
1. 1. Production of Electrolyte Film An electrolyte film was produced by the following method. A 4 wt% polymer solution was prepared by dissolving polyethylene oxide (Mw = 4,000,000 g / mol) in acetonitrile (AN) as a solvent. At this time, LiTFSI was added as a lithium salt together so that [EO] / [Li + ] = 18/1 (molar ratio). The polymer solution was stirred at 60 ° C. overnight so that the PEO and the lithium salt were sufficiently dissolved. Then, an additive solution containing an initiator and a curing agent was prepared. Polyethylene glycol diacrylate (PEGDA, Mw = 575) was used as the curing agent, and benzoyl peroxide (BPO) was used as the initiator. PEGDA was 20 wt% of PEO and BPO was 1 wt% of PEGDA. Acetonitrile was used as the solvent. The mixture was stirred for about 1 hour so that the components to which the additive solution was added were sufficiently mixed. Then, the additive solution was added to the polymer solution, and the two solutions were thoroughly mixed. The mixed solution was applied and coated on the release film using a doctor blade. The coating gap was 800 μm and the coating speed was 20 mm / min. The release film coated with the solution was transferred to a glass plate, dried overnight at room temperature while maintaining horizontality, and vacuum dried at 100 ° C. for 12 hours. Two electrolyte films were obtained by such a method. The thickness of each obtained electrolyte film was about 50 μm.

２．ガイド層が含まれた固体電解質膜の製造
次いで、Ｌｉデンドライトガイド物質として金ナノ粒子（シグマアルドリッチ社製、１００ｎｍ粒径）を、追加的に精製せず、エタノールに分散して分散液を用意した。前記金ナノ粒子の含量は最終的に収得される固体電解質膜の重さ対比１ｗｔ％になるようにした。製造例１で用意した一枚の電解質フィルムの表面に前記分散液をスピンコーティングで塗布し、乾燥して溶媒を除去してガイド層を形成した。その後、製造例１で用意した残り一枚の電解質フィルムを前記ガイド層上に配置してラミネーションし、最終ガイド層が含まれた固体電解質膜を製造した。最終的に得られた固体電解質膜の厚さは約１００μｍであった。 2. 2. Production of a solid electrolyte membrane containing a guide layer Next, gold nanoparticles (manufactured by Sigma-Aldrich, 100 nm particle size) were dispersed in ethanol as a Lidendrite guide substance to prepare a dispersion. .. The content of the gold nanoparticles was set to 1 wt% with respect to the weight of the finally obtained solid electrolyte membrane. The dispersion was applied by spin coating on the surface of one electrolyte film prepared in Production Example 1 and dried to remove the solvent to form a guide layer. Then, the remaining one electrolyte film prepared in Production Example 1 was arranged on the guide layer and laminated to produce a solid electrolyte membrane containing the final guide layer. The thickness of the finally obtained solid electrolyte membrane was about 100 μm.

３．正極の製造
スラリーを製作するため、電極活物質としてのＮＣＭ８１１（ＬｉＮｉ０．８Ｃｏ０．１Ｍｎ０．１Ｏ２）、導電材としてのＶＧＣＦ（気相法炭素繊維（ｖａｐｏｒ ｇｒｏｗｎ ｃａｒｂｏｎ ｆｉｂｅｒ））及び高分子系固体電解質（ＰＥＯ＋ＬｉＴＦＳＩ、［ＥＯ］：［Ｌｉ＋］＝１８：１ｍｏｌ比）を８０：３：１７の重量比で混合し、アセトニトリルに投入して撹拌して電極スラリーを製造した。これを厚さ２０μｍのアルミニウム集電体にドクターブレードを用いて塗布し、その結果物を１２０℃で４時間真空乾燥した。その後、真空乾燥の結果物をロールプレスを用いて圧延工程を行って、２ｍＡｈ／ｃｍ２の電極ローディング、電極層の厚さが４８μｍ、気孔度が２２％である電極を収得した。 3. 3. Manufacture of positive electrode In order to manufacture a slurry, NCM811 (LiNi 0.8 Co 0.1 Mn 0.1 O 2 ) as an electrode active material and VGCF (vapor green carbon fiber) as a conductive material) And a polymer-based solid electrolyte (PEO + LiTFSI, [EO]: [Li + ] = 18: 1 mol ratio) was mixed at a weight ratio of 80: 3: 17, and the mixture was added to acetonitrile and stirred to produce an electrode slurry. This was applied to an aluminum current collector having a thickness of 20 μm using a doctor blade, and the result was vacuum dried at 120 ° C. for 4 hours. Then, the result of vacuum drying was subjected to a rolling step using a roll press to obtain an electrode having an electrode loading of 2 mAh / cm 2 , an electrode layer thickness of 48 μm, and a porosity of 22%.

４．電池の製造
製造された正極を１．４８７５ｃｍ２の円形に打ち抜いて用意した。１．７６７１ｃｍ２の円形で切断したリチウム金属薄膜を対向電極として用意した。二つの電極の間に収得した固体電解質層を介在させてコイン型ハーフセルを製造した。 4. Manufacture of battery The manufactured positive electrode was prepared by punching it into a circle of 1.4875 cm 2 . A lithium metal thin film cut into a circle of 1.7671 cm 2 was prepared as a counter electrode. A coin-shaped half cell was manufactured by interposing a obtained solid electrolyte layer between the two electrodes.

実施例２
Ｌｉデンドライトガイド物質の含量を２ｗｔ％にしたことを除き、実施例１と同じ方法で固体電解質膜を製造した。また、製造された固体電解質膜を用いて実施例１と同じ方法で電池を製造した。 Example 2
A solid electrolyte membrane was produced by the same method as in Example 1 except that the content of the Lidendrite guide substance was 2 wt%. Further, a battery was manufactured by the same method as in Example 1 using the manufactured solid electrolyte membrane.

実施例３
実施例１の製造例１と同じ方法で固体電解質フィルムを三枚用意した。二枚の固体電解質フィルムの表面にガイド層を形成した。ガイド層の形成は実施例１の前記２．と同じ方法で行った。それぞれのガイド層が固体電解質フィルムの間に介在されるように三枚の固体電解質フィルムを積層しラミネーションして固体電解質膜を製造した。その断面構造は固体電解質フィルム／ガイド層／固体電解質フィルム／ガイド層／固体電解質フィルムが順次に積層された形態であった。このようにして製造された固体電解質膜を用いて実施例１の前記３．及び４．と同じ方法で全固体電池を製造した。 Example 3
Three solid electrolyte films were prepared by the same method as in Production Example 1 of Example 1. A guide layer was formed on the surface of the two solid electrolyte films. The guide layer is formed in the above 2. I did it the same way as. Three solid electrolyte films were laminated and laminated so that each guide layer was interposed between the solid electrolyte films to produce a solid electrolyte membrane. The cross-sectional structure was a form in which the solid electrolyte film / guide layer / solid electrolyte film / guide layer / solid electrolyte film were sequentially laminated. Using the solid electrolyte membrane thus produced, the above 3. And 4. The all-solid-state battery was manufactured by the same method as above.

実施例４
Ｌｉデンドライトガイド物質としての銀ナノ粒子（シグマアルドリッチ社製、１００ｎｍ）の含量を２ｗｔ％にしたことを除き、実施例１と同じ方法で固体電解質膜を製造した。また、製造された固体電解質膜を用いて実施例１と同じ方法で電池を製造した。 Example 4
A solid electrolyte membrane was produced by the same method as in Example 1 except that the content of silver nanoparticles (manufactured by Sigma-Aldrich, 100 nm) as a Lidendrite guide substance was set to 2 wt%. Further, a battery was manufactured by the same method as in Example 1 using the manufactured solid electrolyte membrane.

比較例１
Ｌｉデンドライトガイド物質を含まないことを除き、実施例１と同じ方法で固体電解質膜を製造した。また、製造された固体電解質膜を用いて実施例１と同じ方法で電池を製造した。 Comparative Example 1
A solid electrolyte membrane was produced by the same method as in Example 1 except that it did not contain a Lidendrite guide substance. Further, a battery was manufactured by the same method as in Example 1 using the manufactured solid electrolyte membrane.

比較例２
Ｌｉデンドライトガイド物質を含まないことを除き、実施例３と同じ方法で固体電解質膜を製造した。また、製造された固体電解質膜を用いて実施例１と同じ方法で電池を製造した。 Comparative Example 2
A solid electrolyte membrane was produced by the same method as in Example 3 except that it did not contain a Lidendrite guide substance. Further, a battery was manufactured by the same method as in Example 1 using the manufactured solid electrolyte membrane.

実験例１：固体電解質膜のイオン伝導度の評価
それぞれの実施例及び比較例で製作された固体電解質膜を１．７６７１ｃｍ２の円形で切断した。これを二枚のステンレス鋼（ＳＵＳ）の間に配置してコインセルを製作した。分析装置（ＶＭＰ３、バイオロジック社製）を使用して６０℃、振幅１０ｍＶ及びスキャンレンジ５００ｋＨｚ～２０ＭＨｚの条件で電気化学的インピーダンスを測定し、それに基づいてイオン伝導度を計算した。 Experimental Example 1: Evaluation of Ion Conductivity of Solid Electrolyte Film The solid electrolyte membrane produced in each Example and Comparative Example was cut into a circle of 1.7671 cm 2 . This was placed between two pieces of stainless steel (SUS) to make a coin cell. The electrochemical impedance was measured under the conditions of 60 ° C., an amplitude of 10 mV and a scan range of 500 kHz to 20 MHz using an analyzer (VMP3, manufactured by Biologic), and the ionic conductivity was calculated based on the measurement.

実験例２：初期放電容量及び寿命特性の評価
実施例１～４及び比較例１、２で製造した電池に対し、６０℃、０．０５Ｃで充電及び放電を行って初期放電容量を評価した。 Experimental Example 2: Evaluation of initial discharge capacity and life characteristics The initial discharge capacity was evaluated by charging and discharging the batteries manufactured in Examples 1 to 4 and Comparative Examples 1 and 2 at 60 ° C. and 0.05 C.

充電条件：ＣＣ（定電流）／ＣＶ（定電圧）、（４．１５Ｖ、０．００５Ｃで電流カットオフ）
放電条件：ＣＣ（定電流）条件３Ｖ、（０．０５Ｃ） Charging conditions: CC (constant current) / CV (constant voltage), (current cutoff at 4.15V, 0.005C)
Discharge condition: CC (constant current) condition 3V, (0.05C)

一方、短絡発生時点は、０．１Ｃで充放電を行って寿命を評価するとき、充電中の電圧の非正常挙動（不安定な電圧変化）時点をもって判断した。 On the other hand, the time point at which a short circuit occurs was determined based on the time point of abnormal behavior (unstable voltage change) of the voltage during charging when charging and discharging at 0.1 C to evaluate the life.

Figure 2022529975000002
Figure 2022529975000002

表１から確認できるように、本発明の実施例１～実施例４の電池寿命特性が比較例の電池に比べて優れることが分かる。特に、少量のＬｉデンドライトガイド物質を添加した場合でもイオン伝導度の減少は僅かである一方、寿命特性は画期的に改善された。これは誘導（ガイド）物質が種結晶の役割を十分に果たした結果、リチウムデンドライトの成長が、固体電解質膜の厚さ方向ではなく、面方向に誘導されたためであると解釈される。 As can be confirmed from Table 1, it can be seen that the battery life characteristics of Examples 1 to 4 of the present invention are superior to those of the batteries of Comparative Examples. In particular, even when a small amount of Lidendrite guide material was added, the decrease in ionic conductivity was slight, but the lifetime characteristics were dramatically improved. It is interpreted that this is because the growth of the lithium dendrite is induced not in the thickness direction of the solid electrolyte membrane but in the plane direction as a result of the inducing (guide) substance sufficiently playing the role of the seed crystal.

１０：従来の全固体電池、１１：正極集電体、１２：正極活物質層、１３：固体電解質膜、１４：リチウム金属負極、１４ａ：リチウムデンドライト、１００：全固体電池、１１０：正極集電体、１２０：正極活物質層、１３０：固体電解質膜、１３１：金属粒子、１３１ａ：リチウムとの合金、１４０：リチウム金属負極、１４０ａ：リチウムデンドライト、１４０ｂ：水平方向に成長誘導されたリチウムデンドライト 10: Conventional all-solid-state battery, 11: Positive electrode current collector, 12: Positive electrode active material layer, 13: Solid electrolyte film, 14: Lithium metal negative electrode, 14a: Lithium dendrite, 100: All-solid-state battery, 110: Positive electrode current collector Body, 120: Positive electrode active material layer, 130: Solid electrolyte film, 131: Metal particles, 131a: Alloy with lithium, 140: Lithium metal negative electrode, 140a: Lithium dendrite, 140b: Horizontally grown lithium dendrite

Claims (11)

ガイド層を含む固体電解質膜であって、
前記固体電解質膜は、固体電解質材料及び金属粒子を含み、前記金属粒子はリチウムと合金化可能なものであり、
前記ガイド層は、前記固体電解質膜内に層状構造で配置され、前記金属粒子は前記ガイド層に含まれる、全固体電池用固体電解質膜。 A solid electrolyte membrane containing a guide layer,
The solid electrolyte membrane contains a solid electrolyte material and metal particles, and the metal particles can be alloyed with lithium.
The guide layer is arranged in a layered structure in the solid electrolyte membrane, and the metal particles are contained in the guide layer, which is a solid electrolyte membrane for an all-solid-state battery. 前記金属粒子は、リチウム金属核生成過電位が１００ｍＶ以下である、請求項１に記載の全固体電池用固体電解質膜。 The solid electrolyte membrane for an all-solid-state battery according to claim 1, wherein the metal particles have a lithium metal nucleation superpotential of 100 mV or less. 前記固体電解質膜は、金属粒子としてＡｕ、Ａｇ、Ｐｔ、Ｚｎ、Ｍｇ、Ａｌ、Ｎｉ、Ｂｉまたはこれらのうち二つ以上を含む、請求項１または２に記載の全固体電池用固体電解質膜。 The solid electrolyte membrane for an all-solid-state battery according to claim 1 or 2, wherein the solid electrolyte membrane contains Au, Ag, Pt, Zn, Mg, Al, Ni, Bi or two or more of these as metal particles. 前記ガイド層は、厚さが１ｎｍ～１，０００ｎｍである、請求項１から３のいずれか一項に記載の全固体電池用固体電解質膜。 The solid electrolyte membrane for an all-solid-state battery according to any one of claims 1 to 3, wherein the guide layer has a thickness of 1 nm to 1,000 nm. 前記固体電解質材料は、高分子系固体電解質材料を含む、請求項１から４のいずれか一項に記載の全固体電池用固体電解質膜。 The solid electrolyte membrane for an all-solid-state battery according to any one of claims 1 to 4, wherein the solid electrolyte material includes a polymer-based solid electrolyte material. 前記高分子系固体電解質材料は、高分子樹脂及びリチウム塩を含み、１×１０－７Ｓ／ｃｍ以上のイオン伝導度を有する、請求項５に記載の全固体電池用固体電解質膜。 The solid electrolyte membrane for an all-solid-state battery according to claim 5, wherein the polymer-based solid electrolyte material contains a polymer resin and a lithium salt and has an ionic conductivity of 1 × 10 -7 S / cm or more. 前記金属粒子は、粒径が１ｎｍ～５μｍである、請求項１に記載の全固体電池用固体電解質膜。 The solid electrolyte membrane for an all-solid-state battery according to claim 1, wherein the metal particles have a particle size of 1 nm to 5 μm. 前記金属粒子は、固体電解質膜１００重量％に対して０．１ｗｔ％～２０ｗｔ％の比率で含まれる、請求項１に記載の全固体電池用固体電解質膜。 The solid electrolyte membrane for an all-solid-state battery according to claim 1, wherein the metal particles are contained in a ratio of 0.1 wt% to 20 wt% with respect to 100% by weight of the solid electrolyte membrane. 請求項１から８のいずれか一項に記載の固体電解質膜を含む全固体電池。 An all-solid-state battery comprising the solid electrolyte membrane according to any one of claims 1 to 8. 前記全固体電池は、負極が負極活物質としてリチウム金属を含むか又は負極活物質なしに集電体のみからなる、請求項９に記載の全固体電池。 The all-solid-state battery according to claim 9, wherein the all-solid-state battery contains a lithium metal as a negative electrode active material or consists only of a current collector without a negative electrode active material. 前記全固体電池は、負極、正極及び固体電解質膜を含み、前記固体電解質膜は負極と正極との間に介在され、前記負極及び正極の一つ以上は固体電解質材料を含み、前記固体電解質材料は高分子系固体電解質、酸化物系固体電解質、硫化物系固体電解質またはこれらのうち二つ以上を含む、請求項９に記載の全固体電池。 The all-solid battery includes a negative electrode, a positive electrode and a solid electrolyte membrane, the solid electrolyte film is interposed between the negative electrode and the positive electrode, and one or more of the negative electrode and the positive electrode contains a solid electrolyte material, and the solid electrolyte material. The all-solid-state battery according to claim 9, which comprises a polymer-based solid electrolyte, an oxide-based solid electrolyte, a sulfide-based solid electrolyte, or two or more of them.
JP2021561994A 2019-04-19 2020-04-20 Electrolyte membrane for all-solid-state battery and all-solid-state battery including the same Active JP7263551B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
KR1020190046310A KR20200122904A (en) 2019-04-19 2019-04-19 A electrolyte membrane for all solid-state battery and an all solid-state battery comprising the same
KR10-2019-0046310 2019-04-19
PCT/KR2020/005231 WO2020214010A1 (en) 2019-04-19 2020-04-20 Electrolyte membrane for all-solid-state battery and all-solid-state battery comprising same

Publications (2)

Publication Number Publication Date
JP2022529975A true JP2022529975A (en) 2022-06-27
JP7263551B2 JP7263551B2 (en) 2023-04-24

Family

ID=72838171

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2021561994A Active JP7263551B2 (en) 2019-04-19 2020-04-20 Electrolyte membrane for all-solid-state battery and all-solid-state battery including the same

Country Status (6)

Country Link
US (1) US20220200097A1 (en)
EP (1) EP3955362A1 (en)
JP (1) JP7263551B2 (en)
KR (1) KR20200122904A (en)
CN (1) CN113892205A (en)
WO (1) WO2020214010A1 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112166520A (en) * 2018-06-15 2021-01-01 株式会社Lg化学 Solid electrolyte membrane and solid-state battery including the same
KR20200122660A (en) * 2019-04-18 2020-10-28 주식회사 엘지화학 A electrolyte membrane for all solid-state battery and an all solid-state battery comprising the same
WO2020226334A1 (en) * 2019-05-03 2020-11-12 주식회사 엘지화학 Solid electrolyte membrane and solid-state battery comprising same
WO2023106852A1 (en) * 2021-12-08 2023-06-15 주식회사 엘지에너지솔루션 Solid electrolyte and method for producing same
KR102651788B1 (en) * 2021-12-08 2024-03-27 주식회사 엘지에너지솔루션 Solid electrolyte and method for preparing the same
WO2023106849A1 (en) * 2021-12-08 2023-06-15 주식회사 엘지에너지솔루션 Solid electrolyte and preparation method therefor

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4393124A (en) * 1981-10-05 1983-07-12 The United States Of America As Represented By The United States Department Of Energy Solid electrolytes strengthened by metal dispersions
JP2014534553A (en) * 2011-09-27 2014-12-18 シーメンス アクチエンゲゼルシヤフトＳｉｅｍｅｎｓ Ａｋｔｉｅｎｇｅｓｅｌｌｓｃｈａｆｔ Accumulating member and method for producing the accumulating member
US20150118572A1 (en) * 2013-10-29 2015-04-30 Battery Energy Storage Systems-Technologies Solid-state battery and methods of fabrication
JP2019505074A (en) * 2016-02-03 2019-02-21 コリア インスティテュート オブ インダストリアル テクノロジーＫｏｒｅａ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｉｎｄｕｓｔｒｉａｌ Ｔｅｃｈｎｏｌｏｇｙ ALL-SOLID LITHIUM SECONDARY BATTERY INCLUDING LLZO SOLID ELECTROLYTE AND METHOD FOR PRODUCING THE SAME
JP2019061867A (en) * 2017-09-27 2019-04-18 セイコーエプソン株式会社 Lithium battery, method of manufacturing lithium battery, and electronic apparatus

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06310125A (en) * 1993-04-20 1994-11-04 Mitsubishi Cable Ind Ltd Negative electrode for lithium secondary battery
KR20160002988A (en) * 2013-04-23 2016-01-08 어플라이드 머티어리얼스, 인코포레이티드 Electrochemical cell with solid and liquid electrolytes
US20140335429A1 (en) * 2013-05-10 2014-11-13 Zinc Air Fuel Cells, Inc. Alkaline battery with electrolyte gradient
KR101592812B1 (en) * 2015-01-30 2016-02-05 현대자동차주식회사 Secondary cell battery and a manufacturing method thereof
WO2018180768A1 (en) * 2017-03-31 2018-10-04 倉敷紡績株式会社 Electrode sheet, all-solid battery, manufacturing method for electrode sheet, and manufacturing method for all-solid battery
KR102448929B1 (en) * 2017-05-10 2022-09-30 한국전자통신연구원 Method for manufacturing electrode structure for lithium battery and method for manufacturing lithium battery using the same
CN109659474A (en) * 2017-10-12 2019-04-19 宁德时代新能源科技股份有限公司 Rigid diaphragm and solid-state lithium metal battery
KR20190046310A (en) 2017-10-26 2019-05-07 주식회사 이엠맵정보 CCTV Camera Video Fault Management System
KR20200122660A (en) * 2019-04-18 2020-10-28 주식회사 엘지화학 A electrolyte membrane for all solid-state battery and an all solid-state battery comprising the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4393124A (en) * 1981-10-05 1983-07-12 The United States Of America As Represented By The United States Department Of Energy Solid electrolytes strengthened by metal dispersions
JP2014534553A (en) * 2011-09-27 2014-12-18 シーメンス アクチエンゲゼルシヤフトＳｉｅｍｅｎｓ Ａｋｔｉｅｎｇｅｓｅｌｌｓｃｈａｆｔ Accumulating member and method for producing the accumulating member
US20150118572A1 (en) * 2013-10-29 2015-04-30 Battery Energy Storage Systems-Technologies Solid-state battery and methods of fabrication
JP2019505074A (en) * 2016-02-03 2019-02-21 コリア インスティテュート オブ インダストリアル テクノロジーＫｏｒｅａ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｉｎｄｕｓｔｒｉａｌ Ｔｅｃｈｎｏｌｏｇｙ ALL-SOLID LITHIUM SECONDARY BATTERY INCLUDING LLZO SOLID ELECTROLYTE AND METHOD FOR PRODUCING THE SAME
JP2019061867A (en) * 2017-09-27 2019-04-18 セイコーエプソン株式会社 Lithium battery, method of manufacturing lithium battery, and electronic apparatus

Also Published As

Publication number Publication date
KR20200122904A (en) 2020-10-28
EP3955362A4 (en) 2022-02-16
JP7263551B2 (en) 2023-04-24
EP3955362A1 (en) 2022-02-16
CN113892205A (en) 2022-01-04
WO2020214010A1 (en) 2020-10-22
US20220200097A1 (en) 2022-06-23

Similar Documents

Publication Publication Date Title
KR101747864B1 (en) Composite electrolyte, and lithium battery comprising electrolyte
JP7263551B2 (en) Electrolyte membrane for all-solid-state battery and all-solid-state battery including the same
JP7102556B2 (en) Solid electrolyte membrane and all-solid-state battery containing it
KR101749508B1 (en) Electrode active material for lithium secondary battery, electrode for lithium secondary battery including the same, and lithium secondary battery comprising the same
JP7183398B2 (en) Electrolyte membrane for all-solid-state battery and manufacturing method thereof
KR20170050561A (en) Semi-Interpenetrating Polymer Networks Polymer Electrolyte and All-Solid-State Battery comprising The Same
JP7222096B2 (en) Electrolyte membrane for all-solid-state battery and all-solid-state battery including the same
JP2022513248A (en) Electrolyte membrane for all-solid-state battery and all-solid-state battery containing it
KR20210059662A (en) A solid electrolyte mambrane and all solid sate lithium secondary battery including the same
JP2021533543A (en) Solid electrolyte membrane and all-solid-state battery containing it
US11876247B2 (en) Electrolyte membrane for all-solid-state battery, and all-solid-state battery including same
JP7399191B2 (en) Solid electrolyte membrane and all-solid battery containing it
KR20200078228A (en) A solid electrolyte layer and an all-solid-state battery comprising the same
KR102491164B1 (en) A solid electrolyte membrane and a method for manufacturing the same and an all solid state lithium secondary battery comprising the same
US11811043B2 (en) Electrode for all-solid-state battery and method for manufacturing electrode assembly comprising the same
KR102413379B1 (en) A solid electrolyte layer and an all-solid-state battery comprising the same
KR20190129768A (en) A solid electrolyte layer and an all-solid-state battery comprising the same
KR102298058B1 (en) A solid electrolyte layer and an all-solid-state battery comprising the same
JP2023511031A (en) ALL-SOLID BATTERY AND METHOD FOR MANUFACTURING ALL-SOLID BATTERY
KR20220018189A (en) Anode active material for secondary battery comprising layer ion exchanged into Li+ and method for manufacturing the same
KR20200127769A (en) A solid electrolyte membrane and an all solid state lithium secondary battery comprising the same

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20211018

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20221019

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20221128

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20230215

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20230327

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20230412

R150 Certificate of patent or registration of utility model

Ref document number: 7263551

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150